CN106117468B - The preparation method of the high anti-chamotte mould cement water reducing agent of graft copolymerization cationic side chain - Google Patents
The preparation method of the high anti-chamotte mould cement water reducing agent of graft copolymerization cationic side chain Download PDFInfo
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F271/00—Macromolecular compounds obtained by polymerising monomers on to polymers of nitrogen-containing monomers as defined in group C08F26/00
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/16—Sulfur-containing compounds
- C04B24/161—Macromolecular compounds comprising sulfonate or sulfate groups
- C04B24/163—Macromolecular compounds comprising sulfonate or sulfate groups obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/165—Macromolecular compounds comprising sulfonate or sulfate groups obtained by reactions only involving carbon-to-carbon unsaturated bonds containing polyether side chains
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- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/2664—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of ethylenically unsaturated dicarboxylic acid polymers, e.g. maleic anhydride copolymers
- C04B24/267—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of ethylenically unsaturated dicarboxylic acid polymers, e.g. maleic anhydride copolymers containing polyether side chains
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- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
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- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
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- C08F4/00—Polymerisation catalysts
- C08F4/40—Redox systems
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- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
- C04B2103/302—Water reducers
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Abstract
The preparation method of the high anti-chamotte mould cement water reducing agent of graft copolymerization cationic side chain belongs to water reducer field.The present invention polymerize the high anti-chamotte mould cement water reducing agent material of the method synthesis graft copolymerization cationic side chain of resterification reaction then graft copolymerization by first cationic side chain, i.e. using unsaturated cationic quaternary ammonium salt monomer as reactant, radical polymerization obtains terminal hydroxy group cationic side chain under the redox initiation system of high price cerium salt and alcohols composition, then by unsaturated carboxylic acid, terminal hydroxy group cationic side chain, poly glycol monomethyl ether carries out esterification in the presence of catalyst and generates two kinds of polymeric monomers, again with unsaturated carboxylic acid class monomer, cationic side chain polymeric monomer, polyether lateral chain polymeric monomer is reactant, radical graft copolymerization reaction is carried out under initiator and chain-transferring agent effect to be made.Process of the present invention step is simple, efficient quick, regulation and control are convenient, energy-conserving and environment-protective, and innovation synthesizes compound side-chain structure, realizes that diminishing protects the effect of collapsing and suppressing side effect of clay.
Description
Technical field
The present invention relates to a kind of technical field of the high anti-chamotte mould water reducer of cement concrete, a kind of use is related specifically to
Unsaturated cation quaternary ammonium salt first polymerize again with esters of unsaturated carboxylic acids chemical conversion for side chain polymeric monomer then with the small list of unsaturated carboxylic acid
The specific preparation method of the high anti-chamotte mould cement water reducing agent of body graft copolymerization synthesis.
Background technology
High performance concrete and flourishing for concrete chemical admixture cause objectively to concrete and its each component
Performance requirement more and more higher, researchers, which are directed to exploitation, at present can be obviously improved the property such as workability of concrete, durability
The chemical admixture of energy, however, concrete raw material especially fills to the application performance important of chemical admixture
The a small amount of clay brought into during aggregate can have negative effect to mobility, intensity, durability of concrete etc., and this has turned into
Restrict keeping in check for concrete chemical admixture popularization and application.
At present, the high-quality sandstone of extremely low clay content is extremely rare, directly affects pouring for ready-mixed concrete industry
Quality is built, it has been the task of top priority to develop a kind of high anti-chamotte mould water reducer of cement concrete.The maximum of polymer electrolyte diminishing water reducer
Advantage is can be by exchanging polymerized monomer species, changing monomer match ratio and set the methods of regulatory molecule structure functional group
Different molecular structures and the product of performance are counted out, thus are the diminishings that a kind of structure design flexibility ratio is big, performance regulation and control space is big
Agent kind.Therefore, cement water reducing agent research and application it is more and more extensive, constantly move towards high-effect and multi-functional industry
Change application.
Subject crossing is realized by the Molecular Design method of cement water reducing agent polymer, development can suppress the secondary work of clay
High anti-chamotte mould water reducer, the not only excellent service behaviour with conventional water reducing agents, while also there is resistance side effect of clay
Peculiar advantage feature, can fully alleviate the imbalance between supply and demand of high-quality aggregate, realize ecological environmental protection and natural resources energy-conservation
Consumption reduction, shows good application prospect.
Patent CN 104311743A (publication date：On January 28th, 2015) report a kind of low cost for wastewater treatment
The preparation method of modified flocculant.The invention is used as initiator initiation based on hydroxymethyl starch, by adding ammonium ceric nitrate
Acrylamide monomer reacts to obtain modified flocculant with formaldehyde and dimethylamine again in hydroxymethyl starch surface grafting polymerization, product.
The advantages of invention be using the extensive hydroxymethyl starch in source as key reaction raw material, cost is cheap, the pH value scope of application is wide,
Flocculating property is excellent, and the ammonium ceric nitrate initiator used can also effectively utilize the advantage of the initiation system.But should
Invention product neither possesses the scattered ability of diminishing, does not also possess high anti-mud effect, therefore although utilize as excellent flocculant
The initiation system of ammonium ceric nitrate, still it can not be applied in the field of agent on crack resistance of concrete mud water reducer.
Patent CN104446101A (publication date：On March 25th, 2015) report a kind of cation-modified polycarboxylic acids and subtract
Aqua, it is by isoamyl alcohol polyoxyethylene ether monomer, unitary unsaturated carboxylic acid and its derivatives monomer, cationic monomer and two
The combined polymerization in the presence of initiator and chain-transferring agent of first unsaturated carboxylic acid and its derivatives monomer forms.The invention product adds
During into concrete, it can simultaneously adsorb on positively charged and negatively charged cement minerals surface, embody and be superior to anion
The characteristics of type polycarboxylate water-reducer, moreover, product strand in cement slurry alkaline environment extends, absorption shape is more
Unfold, water-reducing rate is more excellent.But the invention product is only to introduce cationic monomer in the main chain of molecular structure, is carried
High diminishing dispersion effect necessarily, and be not implemented while diminishing disperses and show high anti-mud performance etc. and apply feature,
Fail to realize complex functionality chemical admixture by Molecular Design method.
Patent CN 104402292A (publication date：On March 11st, 2015) report a kind of preparation of modified starch water reducer
Method.The patent is using starch as primary raw material, carries out degradation modification with oxidant and sodium carbonate, then adds monomer and initiation
Agent carries out graft polymerization and prepares modified starch water reducer, and water-reducing rate is 3-4 hours more than 26%, Slow setting time, can be effectively
Phenomena such as preventing bleeding, isolation.The advantages of invention be using the native starch of safety and environmental protection and wide material sources as reaction raw materials,
Realizing reduces the purpose of cost, simultaneously as it is partially modified in structure, therefore cement can also be improved to a certain extent
The workability of concrete and the adaptability containing argillaceous sand stone.But the invention product still needs with starching gathering in mortar concrete only
The additives such as carboxylic acid water reducer are used cooperatively, and are failed the dual-use function of compound diminishing-anti-mud, are not had the only of function integration
Special advantage, the water reducer of New function type can not be opened up from structural nature aspect.
Concrete diminishing water reducer described in most patents has been provided with good mobility, water-retaining property, cohesiveness etc.
Service behaviour.However, above-mentioned synthetic method has a certain degree of weak point, researcher focus mostly in realize diminishing it is scattered,
Anti- mud, flocculation a certain item performance therein, and seldom pass through graft polymerization cationic side chain under high price cerium salt inducement system
Method realizes that integrating diminishing-guarantor is collapsed-disperses-complex function type chemical admixture of the application performance such as anti-mud.Only by
Simple backbone modification or synthetic starch base diminishing diminishing agent material limit its popularization in water reducer of cement concrete field
Using through fact proved that complex function group type molecular structure of the synthesis with multiple action can significantly improve the application of polymer
Performance effects.Therefore, this requires the water reducer of cement concrete of synthesis to realize the innovation of molecular structure, not only to possess diminishing
- compound the service behaviour of anti-mud of collapsing is protected, while also can guarantee that easily technological operation, cheap preparation cost, simple and easy to get
Reaction raw materials, be advantageous to industrialized production and popularization and application, relevant this respect work has no report both at home and abroad.
The content of the invention
It is an object of the invention to provide a kind of synthesis of the high anti-chamotte mould cement water reducing agent of graft copolymerization cationic side chain
Technique, it polymerize unsaturated cationic quaternary ammonium salt monomer by the way that high price cerium salt is formed into oxidation-reduction trigger system initiation with alcohols
Terminal hydroxy group cationic side chain is obtained, is then esterified terminal hydroxy group cationic side chain, poly glycol monomethyl ether and unsaturated carboxylic acid
To cation polymeric monomer and polyether macromonomer, then both polymeric monomers are subjected to free radical grafting with unsaturated carboxylic acid minor comonomer and are total to
It is poly- to obtain the high anti-chamotte mould cement concrete water reducer of excellent performance.The present invention is from design theory of molecular structure, is increased
Added using high price cerium salt -ol as redox initiation system under polymeric cationic side chain the step of and successfully realize grafting altogether
It is poly-, carboxylic acid monomer and cation polymeric monomer side chain, polyether macromonomer side chain combined polymerization are joined together to form with high diminishing
With the new polycarboxylic acid water reducer of the multiple action effect such as high anti-mud, its work is improved by side chain molecular structure innovation realization
The purpose of efficiency, enrich application of the polymer architecture-performance study in concrete chemical admixture field.Closed using this method
Into cement concrete water reducer there is compound side-chain structure, formed different from the side chain of conventional polycarboxylate water-reducer, it is poly-
Ether side chain can be acted on by steric hindrance and realize that excellent diminishing protects effect of collapsing, and its cationic side chain structure is in high clay content
Concrete system in can also change charge characteristic, further prevent polyether lateral chain is adsorbed to enter clay interlayer, Ke Yiyou
Effect suppresses clay to adverse effect caused by dispersion flows performance, shows the work more more excellent than common polycarboxylate water-reducer
Characteristic and action effect.
The invention provides a kind of preparation method of the high anti-chamotte mould cement water reducing agent of graft copolymerization cationic side chain, leads to
Cross the high anti-chamotte mould cement water reducing agent material of method synthesis of first cationic side chain polymerization resterification reaction then graft copolymerization, bag
Include following condition and step：
(1) cationic side chain polymerize：Monomer unsaturation cation quaternary ammonium salt and reducing agent lower aliphatic alcohols are added first
In reactor, add water and be configured to the aqueous solution that mass concentration is 2-10%, reactor inflated with nitrogen 3-5 deoxygenation 10- repeatedly
Sealed after 30 minutes, add oxidant high price cerium salt, stirring 10-30 minutes treat that it is well mixed, are continuously heating at 10-60 DEG C
Polymerisation is carried out, 6-16 hours is reacted, produces the terminal hydroxy group cationic side chain aqueous solution；
(2) esterification：Step (1) products therefrom terminal hydroxy group cationic side chain aqueous solution is mutually mixed with (methyl) acrylic acid
Close, add poly glycol monomethyl ether, be warming up to 50-70 DEG C, treat that poly glycol monomethyl ether is in a liquid state, vacuumize in removing system
Moisture, catalyst is added, stir 5-20 minutes, temperature is increased to add water entrainer at 80-100 DEG C, is continuously heating to 100-150
Carry out esterification at DEG C, reaction gained water is separated while reaction, sloughed after reacting 2-10 hours by vacuumizing
Water entrainer, obtain esterification reaction product；
(3) graft copolymerization：(methyl) acrylic acid or itself and insatiable hunger are sequentially added into esterification reaction product obtained by step (2)
The initiator persulfate aqueous solution that mixture, water, molecular weight regulator, mass fraction with carboxylic acid are 1-30%, and often
Secondary feeding interval mixing time 5-20 minutes, it is warming up at 55-90 DEG C and carries out polymerisation, reacts 1.5-8 hours, be cooled to
25-40 DEG C, it is eventually adding the cement water reducing agent solution that water dilutes the graft copolymerization cationic side chain for producing required concentration.
Unsaturated cation quaternary ammonium salt described in above-mentioned steps (1) is trimethylallylammonium chloride, dimethyl diene
Propyl ammonium chloride, tetra allyl ammonium chloride, acrylyl oxy-ethyl-trimethyl salmiac, methylacryoyloxyethyl trimethyl ammonia chloride
Ammonium, methacryl hydroxypropyltrimonium chloride, acryloxyethyldimethyl butylammonium bromide, methylacryoyloxyethyl two
Methyl butyl ammonium bromide, acryloxyethyldimethyl dodecyl bromination ammonium, methylacryoyloxyethyl dimethyl dodecyl
Base ammonium bromide, acryloxyethyldimethyl cetyl ammonium bromide, methylacryoyloxyethyl dimethyl hexadecyl bromide
One or more in ammonium, dosage and the mol ratio of the high price cerium salt described in step (1) are 10-1000：1；Institute in step (1)
The lower aliphatic alcohols stated are normal propyl alcohol, isopropanol, n-butanol, isobutanol, n-amyl alcohol, 2-methyl-1-butene alcohol, 3- methyl isophthalic acids-fourth
Alcohol, 2,2- dimethyl -1- propyl alcohol or cyclohexanol；High price cerium salt described in step (1) is ammonium ceric nitrate or Cericammoniumsulfate, dosage
Mol ratio with the lower aliphatic alcohols described in step (1) is 0.03-1：1.
In the lower aliphatic alcohols and step (2) described in (methyl) acrylic acid and step (1) described in above-mentioned steps (2)
The total moles ratio of described poly glycol monomethyl ether is 1.5-5：1；Poly glycol monomethyl ether and step described in step (2)
(1) mol ratio of the lower aliphatic alcohols described in is 1-5：1；Catalyst described in step (2) is p-methyl benzenesulfonic acid, phosphoric acid or
Sulfamic acid, dosage are the 2.5-20% of the poly glycol monomethyl ether quality described in step (2)；Band described in step (2)
Aqua is hexamethylene, benzene or toluene, and dosage is the 8-30% of reactant gross mass in esterification, and signified reactant is step
(1) described in products therefrom terminal hydroxy group cationic side chain in, the poly glycol monomethyl ether described in step (2) and step (2)
(methyl) acrylic acid.
Unsaturated carboxylic acid described in above-mentioned steps (3) is itaconic acid, maleic acid (acid anhydride), one kind in fumaric acid or several
Kind, dosage and the mol ratio of (methyl) acrylic acid described in step (3) they are 0.1-5：1；(methyl) third described in step (3)
Olefin(e) acid or its mixture and the lower aliphatic alcohols described in step (1) and the poly- second described in step (2) with unsaturated carboxylic acid
The total moles ratio of glycol monomethyl ether is 1.5-4：1；The quality of addition water described in step (3) is (first described in step (3)
Base) esterification reaction product quality obtained by acrylic acid or its mixture and step (2) with unsaturated carboxylic acid and 80-200%；Step
Suddenly the molecular weight regulator described in (3) is TGA, mercaptopropionic acid, methylpropene sodium sulfonate, ALS or just
Lauryl mercaptan, the lower aliphatic alcohols described in dosage and step (1) and the poly glycol monomethyl ether described in step (2)
Total moles ratio is 0.1-0.4：1；Initiator persulfate described in step (3) is ammonium persulfate, potassium peroxydisulfate or persulfuric acid
Sodium, dosage and the total moles ratio of the lower aliphatic alcohols described in step (1) and the poly glycol monomethyl ether described in step (2) are
0.05-0.25：1.
The number-average molecular weight of poly glycol monomethyl ether in the inventive method is 500-3000.
The inventive method has the advantages that compared with prior art：
1. the present invention is from design theory of molecular structure, using unsaturated cationic quaternary ammonium salt monomer as reactant, in height
Valency cerium salt obtains cationic side chain with radical polymerization under the oxidation-reduction trigger system of alcohol composition, and this is the polyethers from routine
Side chain is on comb shape diminishing water reducer molecular structure direction to the unique design of diversification, the compound side chain development of multifunction
Innovation and breakthrough, its novel special structure can not only realize change of the water reducer in terms of application performance, and favorably
In the intension of theory for expanding Polymer supported catalyst-structure-performance, subsequently to develop other new varieties concrete to a deeper level
Water reducer has widened Research Thinking and developing direction.
2. the inventive method innovatively uses the redox initiation system of high price cerium salt -ol class, high price cerium salt is utilized
Strong oxidizing property and the characteristic for possessing the free free radical of initiation organic matter generation, have abandoned traditional one-component hot initiator system, list
One high price cerium salt inducement system, oxidation-reduction trigger system such as hydrogen peroxide-VC systems etc., the polymerization under the initiation system are anti-
Process is answered gently to stablize, side reaction is few, and can substantially reduce the activation energy in polymerization process, has a extensive future,
A kind of new method for triggering polymerization is provided in cement water reducing agent research field.
3. different from being only to be copolymerized a small amount of cationic structural in molecular backbone in other inventive methods, the inventive method
The high anti-chamotte mould cement water reducing agent of the graft copolymerization cationic side chain of synthesis has a large amount of quaternary ammonium salt cationic polymerization macromolecules
Chain, electrostatic adsorption can be produced with the interlayer of electronegative clay particle and surface, be advantageous to absorption in clay interlayer, together
When, the interlamination region volume of clay is not infinitely great, after substantial amounts of cationic side chain has been adsorbed, can avoid other polyethers
Side chain enters clay interlayer, is not lost so as to protect the diminishing of the cement water reducing agent to protect effect of collapsing, it is anti-to show high diminishing, height
The action effect of mud.The product can also diversification expanded application in the field such as fine chemistry industry and surfactant, be a kind of tool
There is the cement concrete water reducer of peculiar advantage and distinguishing feature, there is good application prospect and the market competitiveness.
4. a building-up process energy consumption is low, mild condition, safety and environmental protection, solvent-free murder by poisoning, cleanliness without any pollution, water entrainer used
It can also continue to recycle after liquid separation-standing-separation, greatly reduce wastage of material, saved production cost.Water entrainer
Condensing reflux can also keep the temperature plateau of reaction system, and can reduce the viscosity of reaction system, make to be stirred more equal
It is even abundant, improve the esterification yield and reaction rate of system.Meanwhile unsaturated carboxylic acid class monomer, (methyl) acrylic acid list used
Body, the suitable molecular weight scope of cation quaternary ammonium salt raw material monomer are wide, are advantageous to large-scale popularization and the application of Diversified Products, increase
Increase the market share occupancy volume of anti-chamotte mould cement concrete water reducer.
5. synthetic method of the present invention, compared with conventional method, raw material needed for reaction is common to be easy to get, and whole building-up process is simple
Controllable, polymerization used and esterif iotacation step are also normal operations technique, without special operational or expensive auxiliary agent, enrich synthesis
The preparation method of cement concrete chemical admixture, there is the characteristics of obvious efficiently convenient, it is easy to accomplish industrialized production.
The building-up process, without particular/special requirement, and remains with the functional group of high diminishing and the high-thin arch dam effect contained by tradition to equipment, and
Have the advantages that molecule can designed capacity be strong, molecular weight is controllable, narrow molecular weight distribution, the degree of polymerization are high, have promote well it is latent
Power and application value.
6. the high anti-chamotte mould cement according to the inventive method synthesis has than conventional polycarboxylate water-reducer more with water reducer
Excellent workability, diminishing protect collapse ability and anti-mud effect, remain to show preferable mobility and holding in high clay content
Ability, and very strong adaptability is shown to the cement of different cultivars.In addition, the cement water reducing agent Product Status is stable,
It is not stratified after being stood under high concentration, do not crystallized after being stored under low temperature and performance is unaffected.The synthetic method is simple direct
While, products obtained therefrom still has excellent property indices, is advantageous to industrial application, therefore with good
Economic benefit and social benefit.
Embodiment
The present invention is described in further detail with reference to embodiment, but the implementation not limited to this of the present invention.
Embodiment 1
26.19g dimethyl diallyl ammonium chlorides and 0.72g isopropanols are added in reactor first, added
699.2g water is configured to the aqueous solution that mass concentration is 4%, and 4 deoxygenations seal reactor inflated with nitrogen after 15 minutes repeatedly, adds
6.44g Cericammoniumsulfates, stirring treats that it is well mixed for 25 minutes, is continuously heating to carry out polymerisation at 52 DEG C, reacts 10 hours,
Produce the terminal hydroxy group cationic side chain aqueous solution；By the products therefrom terminal hydroxy group cationic side chain aqueous solution and 12.91g methacrylic acids
Mix, add 36g poly glycol monomethyl ethers (molecular weight=2000), be warming up to 65 DEG C, treat poly glycol monomethyl ether (molecule
Amount=2000) it is in a liquid state, moisture in removing system is vacuumized, adds 5.4g phosphoric acid, is stirred 18 minutes, when temperature is increased to 80 DEG C
11.37g benzene is added, is continuously heating to carry out esterification at 135 DEG C, is separated reaction gained water while reaction, instead
Benzene is sloughed by vacuumizing after answering 5 hours, obtains esterification reaction product；1.26g is sequentially added in most backward esterification reaction product
The ammonium persulfate that acrylic acid, 11.38g itaconic acids, 88.24 water, 0.64g mercaptopropionic acids and 5.41g mass fractions are 30% is water-soluble
Liquid, and feeding interval mixing time 18 minutes every time, are warming up at 60 DEG C and carry out polymerisation, react 8 hours, be cooled to 25
DEG C, be eventually adding 40.34g water dilute produce mass fraction be 40% graft copolymerization cationic side chain cement water reducing agent it is molten
Liquid.
Embodiment 2
After the cement water reducing agent solution that the concentration that embodiment 1 is obtained is 40% deposits 300 days at 5 DEG C, it is determined
Implementation result.
Embodiment 3
52.98g methylacryoyloxyethyl dimethylbutyl ammonium bromides and 1.2g cyclohexanol are added in reactor first,
Add 487.62g water and be configured to the aqueous solution that mass concentration is 10%, reactor inflated with nitrogen is repeatedly close after 3 deoxygenations 20 minutes
Envelope, 2.86g Cericammoniumsulfates are added, stirring treats that it is well mixed for 23 minutes, is continuously heating to carry out polymerisation at 10 DEG C, reacts
14.5 hours, produce the terminal hydroxy group cationic side chain aqueous solution；By the products therefrom terminal hydroxy group cationic side chain aqueous solution and 9.3g first
Base acrylic acid mixes, and adds 72g poly glycol monomethyl ethers (molecular weight=1200), is warming up to 70 DEG C, treats polyethyleneglycol
Methyl ether (molecular weight=1200) is in a liquid state, and vacuumizes moisture in removing system, adds 5.76g sulfamic acids, stirs 8 minutes, temperature
10.84g toluene is added when degree is increased to 87 DEG C, is continuously heating to carry out esterification at 110 DEG C, institute will be reacted while reaction
Obtain water to separate, slough toluene by vacuumizing after reacting 10 hours, obtain esterification reaction product；Most backward esterification production
2.96g acrylic acid, 5.35g itaconic acids, 4.78g maleic acids, 2.39g fumaric acid, 301.49 water, 0.66g mercaptos are sequentially added in thing
Guanidine-acetic acid and the sodium persulfate aqueous solution that 19.72g mass fractions are 20%, and feeding interval mixing time 15 minutes every time,
It is warming up at 85 DEG C and carries out polymerisation, react 1.5 hours, be cooled to 40 DEG C, is eventually adding 34.48g water and dilutes and produce quality
Fraction is the cement water reducing agent solution of 30% graft copolymerization cationic side chain.
Embodiment 4
After the cement water reducing agent solution that the concentration that embodiment 3 is obtained is 30% is deposited 40 days at 6 DEG C, measure is in fact
Apply effect.
Embodiment 5
8.14g trimethylallylammonium chlorides and 0.72g normal propyl alcohols are added in reactor first, add 434.1g water
The aqueous solution that mass concentration is 2% is configured to, 4 deoxygenations seal reactor inflated with nitrogen after 23 minutes repeatedly, add 0.33g nitric acid
Cerium ammonium, stirring treats that it is well mixed for 20 minutes, is continuously heating to carry out polymerisation at 37 DEG C, reacts 13 hours, produces end hydroxyl
The base cationic side chain aqueous solution；The products therefrom cationic side chain aqueous solution and 9.68g acrylic acid are mixed, 72g is added and gathers
Glycol monoethyl ether (molecular weight=2400), is warming up to 60 DEG C, treats that poly glycol monomethyl ether (molecular weight=2400) is in a liquid state, takes out
Moisture in system is removed in vacuum, adds 7.92g p-methyl benzenesulfonic acid, stirs 12 minutes, temperature is increased to add 18.11g at 90 DEG C
Hexamethylene, it is continuously heating to carry out esterification at 125 DEG C, reaction gained water is separated while reaction, reacted 6 hours
Hexamethylene is sloughed by vacuumizing afterwards, obtains esterification reaction product；10.85g first is sequentially added in most backward esterification reaction product
Base acrylic acid, 108.39 water, 0.96g TGAs and 9.58g mass fractions are 15% sodium persulfate aqueous solution, and every time
Feeding interval mixing time 12 minutes, is warming up at 75 DEG C and carries out polymerisation, reacts 5 hours, is cooled to 30 DEG C, is eventually adding
35.23g water dilutes the cement water reducing agent solution for producing the graft copolymerization cationic side chain that mass fraction is 40%.
Embodiment 6
The cement water reducing agent solution that the mass fraction that embodiment 5 is obtained is 40% determines it after 5 DEG C are deposited 20 days
Implementation result.
Embodiment 7
35.3g methacryls hydroxypropyltrimonium chloride and 1.06g n-amyl alcohols are added in reactor first, added
5.6.35g water is configured to the aqueous solution that mass concentration is 6.7%, and 4 deoxygenations seal reactor inflated with nitrogen after 30 minutes repeatedly, add
Enter 6.58g ammonium ceric nitrates, stirring treats that it is well mixed for 15 minutes, is continuously heating to carry out polymerisation at 60 DEG C, and reaction 7 is small
When, produce the terminal hydroxy group cationic side chain aqueous solution；The products therefrom cationic side chain aqueous solution and 6.92g acrylic acid are mixed,
Add 36g poly glycol monomethyl ethers (molecular weight=3000), be warming up to 68 DEG C, treat poly glycol monomethyl ether (molecular weight=
3000) it is in a liquid state, vacuumizes moisture in removing system, add 7.2g phosphoric acid, stirs 5 minutes, temperature is increased to add at 93 DEG C
19.73g benzene, it is continuously heating to carry out esterification at 100 DEG C, separates reaction gained water while reaction, reaction 9 is small
When after by vacuumizing slough benzene, obtain esterification reaction product；1.84g propylene is sequentially added in most backward esterification reaction product
Acid, 2.78g itaconic acids, 2.09g maleic anhydrides, 3.71g fumaric acid, 75.76 water, 1.84g n-dodecyl mercaptans and 5.48g matter
The ammonium persulfate aqueous solution that fraction is 25%, and feeding interval mixing time 10 minutes every time are measured, is warming up at 90 DEG C and carries out
Polymerisation, react 2 hours, be cooled to 36 DEG C, be eventually adding 9.26g water and dilute the graft copolymerization for producing that mass fraction is 50%
The cement water reducing agent solution of cationic side chain.
Embodiment 8
The cement water reducing agent solution that the mass fraction that embodiment 7 is obtained is 50% determines it after 6 DEG C are deposited 40 days
Implementation result.
Embodiment 9
49.78g acrylyl oxy-ethyl-trimethyl salmiacs and 0.89g n-butanols are added in reactor first, added
673.13g water is configured to the aqueous solution that mass concentration is 7%, and 3 deoxygenations seal reactor inflated with nitrogen after 25 minutes repeatedly, adds
0.29g Cericammoniumsulfates, stirring treats that it is well mixed for 10 minutes, is continuously heating to carry out polymerisation at 45 DEG C, reacts 6 hours,
Produce the terminal hydroxy group cationic side chain aqueous solution；The products therefrom cationic side chain aqueous solution and 12.11g acrylic acid are mixed, then
36g poly glycol monomethyl ethers (molecular weight=500) are added, 55 DEG C is warming up to, treats that poly glycol monomethyl ether (molecular weight=500) is in
Liquid, moisture in removing system is vacuumized, add 0.9g sulfamic acids, stirred 10 minutes, temperature is increased to add at 100 DEG C
29.63g toluene, it is continuously heating to carry out esterification at 105 DEG C, separates reaction gained water while reaction, reaction 7
Toluene is sloughed by vacuumizing after hour, obtains esterification reaction product；9.86g first is sequentially added in most backward esterification reaction product
Base acrylic acid, 1.12g maleic anhydrides, 87.63 water, 5.31g methylpropene sodium sulfonates and 20g mass fractions are 10% persulfuric acid
Sodium water solution, and feeding interval mixing time 20 minutes every time, are warming up at 55 DEG C and carry out polymerisation, react 7.5 hours,
35 DEG C are cooled to, 3.91g water is eventually adding and dilutes the concrete for producing the graft copolymerization cationic side chain that mass fraction is 50%
Diminishing agent solution.
Embodiment 10
The cement water reducing agent solution that the mass fraction that embodiment 9 is obtained is 50% determines it after 7 DEG C are deposited 40 days
Implementation result.
Embodiment 11
69.72g MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chlorides and 0.89g isobutanols are added in reactor first, then
Add 780.12g water and be configured to the aqueous solution that mass concentration is 8.3%, reactor inflated with nitrogen is repeatedly close after 5 deoxygenations 18 minutes
Envelope, 0.2g ammonium ceric nitrates are added, stirring treats that it is well mixed for 18 minutes, is continuously heating to carry out polymerisation at 30 DEG C, reacts
16 hours, produce the terminal hydroxy group cationic side chain aqueous solution；By the products therefrom cationic side chain aqueous solution and 13.95g metering systems
Acid mixes, and adds 75.6g poly glycol monomethyl ethers (molecular weight=1800), is warming up to 50 DEG C, treats poly glycol monomethyl ether
(molecular weight=1800) are in a liquid state, and vacuumize moisture in removing system, add 13.61g p-methyl benzenesulfonic acid, stir 20 minutes, temperature
16.02g hexamethylenes are added when degree is increased to 82 DEG C, are continuously heating to carry out esterification at 150 DEG C, will reaction while reaction
Gained water is separated, and is sloughed hexamethylene by vacuumizing after reacting 9 hours, is obtained esterification reaction product；Most backward esterification is anti-
Answer and 8.11g acrylic acid, 2.61g fumaric acid, 273.06 water, 2.33g ALSs and 72.99g matter are sequentially added in product
The persulfate aqueous solution that fraction is 1%, and feeding interval mixing time 5 minutes every time are measured, is warming up at 65 DEG C and is gathered
Reaction is closed, reacts 7 hours, is cooled to 28 DEG C, 52.89g water is eventually adding and dilutes the graft copolymerization for producing that mass fraction is 30%
The cement water reducing agent solution of cationic side chain.
Embodiment 12
After the cement water reducing agent solution that the concentration that embodiment 11 is obtained is 30% is deposited 20 days at 6 DEG C, it is determined
Implementation result.
Implementation result：
1. flowing degree of net paste of cement
To investigate mobility of the cement water reducing agent solution for the graft copolymerization cationic side chain that the present invention synthesizes to cement
Action effect, experiment determine under identical volume each embodiment to the paste flowing degree of reference cement.GB/T8077- is pressed in experiment
2012《Methods for testing uniformity of concrete admixture》Carry out, W/C=0.29, volume is the solid volume of folding.From existing commercially available
Traditional comb shape poly carboxylic acid series water reducer (comparative example) is as a comparison sample, and result of the test is shown in Table 1.
The pulp flowage results of property of table 1
From table 1 it follows that the cement water reducing agent solution of the graft copolymerization cationic side chain of the inventive method synthesis,
Under 0.29 ratio of mud and the solid volume of 0.25% folding, excellent dispersibility and cement adaptability can be shown.
2. concrete slump and divergence
Experiment determines divergence and the slump and retention property that each embodiment is shown in concrete system, tests
It the results are shown in Table 2.
The concrete flowability energy result of table 2
From Table 2, it can be seen that the cement water reducing agent solution of the graft copolymerization cationic side chain of the inventive method synthesis
Excellent divergence and the slump and holding capacity can be shown in concrete system.
3. agent on crack resistance of concrete mud performance
Experiment determines divergence and the slump and retention property that each embodiment is shown in concrete system, tests
It the results are shown in Table 3.
The concrete flowability energy result of table 3
From table 3 it is observed that the cement water reducing agent solution of the graft copolymerization cationic side chain of the inventive method synthesis
Preferable divergence and the slump and holding capacity can have been shown under 1.8% clay additive.
Claims (3)
1. the preparation method of the high anti-chamotte mould cement water reducing agent of a kind of graft copolymerization cationic side chain, it is characterised in that pass through
The bar of the high anti-chamotte mould cement water reducing agent material of method synthesis of first cationic side chain polymerization resterification reaction then graft copolymerization
Part and step are as follows：
(1) cationic side chain polymerize：Monomer unsaturation cation quaternary ammonium salt and reducing agent lower aliphatic alcohols are added into reaction first
In device, add water and be configured to the aqueous solution that mass concentration is 2-10%, 10-30 points of the 3-5 deoxygenation repeatedly of reactor inflated with nitrogen
Sealed after clock, add oxidant high price cerium salt, stirring 10-30 minutes treat that it is well mixed, are continuously heating to carry out at 10-60 DEG C
Polymerisation, 6-16 hours are reacted, produce the terminal hydroxy group cationic side chain aqueous solution；
(2) esterification：Step (1) products therefrom terminal hydroxy group cationic side chain aqueous solution is mixed with (methyl) acrylic acid,
Poly glycol monomethyl ether is added, is warming up to 50-70 DEG C, treats that poly glycol monomethyl ether is in a liquid state, vacuumizes water in removing system
Point, catalyst is added, stirs 5-20 minutes, temperature is increased to add water entrainer at 80-100 DEG C, is continuously heating to 100-150 DEG C
Lower carry out esterification, reaction gained water is separated while reaction, react and slough band by vacuumizing after 2-10 hours
Aqua, obtain esterification reaction product；
(3) graft copolymerization：(methyl) acrylic acid or itself and unsaturated carboxylic are sequentially added into esterification reaction product obtained by step (2)
Mixture, water, molecular weight regulator, the initiator persulfate aqueous solution that mass fraction is 1-30% of acid, and add every time
Material interval mixing time 5-20 minutes, it is warming up at 55-90 DEG C and carries out polymerisation, reacts 1.5-8 hours, be cooled to 25-40
DEG C, it is eventually adding the cement water reducing agent solution that water dilutes the graft copolymerization cationic side chain for producing required concentration；
Wherein, the unsaturated cation quaternary ammonium salt described in step (1) is trimethylallylammonium chloride, dimethyl diallyl
Ammonium chloride, tetra allyl ammonium chloride, acrylyl oxy-ethyl-trimethyl salmiac, MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride,
Methacryl hydroxypropyltrimonium chloride, acryloxyethyldimethyl butylammonium bromide, methylacryoyloxyethyl diformazan
Base butylammonium bromide, acryloxyethyldimethyl dodecyl bromination ammonium, methylacryoyloxyethyl dimethyl dodecyl base
Ammonium bromide, acryloxyethyldimethyl cetyl ammonium bromide, methylacryoyloxyethyl dimethyl hexadecyl base ammonium bromide
In one or more, the mol ratio of the high price cerium salt described in dosage and step (1) is 10-1000：1；Described in step (1)
Lower aliphatic alcohols for normal propyl alcohol, isopropanol, n-butanol, isobutanol, n-amyl alcohol, 2-methyl-1-butene alcohol, 3- methyl-1-butanols,
2,2- dimethyl -1- propyl alcohol or cyclohexanol；High price cerium salt described in step (1) is ammonium ceric nitrate or Cericammoniumsulfate, dosage with
The mol ratio of lower aliphatic alcohols described in step (1) is 0.03-1：1；Poly glycol monomethyl ether and step described in step (2)
Suddenly the mol ratio of the lower aliphatic alcohols described in (1) is 1-5：1；Catalyst described in step (2) is p-methyl benzenesulfonic acid, phosphoric acid
Or sulfamic acid, dosage are the 2.5-20% of the poly glycol monomethyl ether quality described in step (2)；Described in step (2)
Water entrainer is hexamethylene, benzene or toluene, and dosage is the 8-30% of reactant gross mass in esterification, and signified reactant is step
Suddenly described in products therefrom terminal hydroxy group cationic side chain in (1), the poly glycol monomethyl ether described in step (2) and step (2)
(methyl) acrylic acid；Unsaturated carboxylic acid described in step (3) is itaconic acid, the one or more in maleic acid, fumaric acid,
Unsaturated carboxylic acid can be added or is added without, when added dosage and mole of (methyl) acrylic acid described in step (3)
Than for 0.1-5：1；The quality of addition water described in step (3) be (methyl) acrylic acid described in step (3) or its with not
The 80-200% of esterification reaction product quality sum obtained by the mixture and step (2) of saturated carboxylic acid；Molecule described in step (3)
Amount conditioning agent is TGA, mercaptopropionic acid, methylpropene sodium sulfonate, ALS or n-dodecyl mercaptan, dosage
Total moles ratio with the lower aliphatic alcohols described in step (1) and the poly glycol monomethyl ether described in step (2) is 0.1-
0.4：1；Initiator persulfate described in step (3) is ammonium persulfate, potassium peroxydisulfate or sodium peroxydisulfate, dosage and step
(1) the total moles ratio of the poly glycol monomethyl ether described in lower aliphatic alcohols and step (2) described in is 0.05-0.25：1.
A kind of 2. preparation side of the high anti-chamotte mould cement water reducing agent of graft copolymerization cationic side chain according to claim 1
Method, it is characterised in that (methyl) acrylic acid described in step (2) and the lower aliphatic alcohols and step (2) described in step (1)
Described in the total moles ratio of poly glycol monomethyl ether be 1.5-5：1.
A kind of 3. preparation side of the high anti-chamotte mould cement water reducing agent of graft copolymerization cationic side chain according to claim 1
Method, it is characterised in that (methyl) acrylic acid or its mixture with unsaturated carboxylic acid and institute in step (1) described in step (3)
The total moles ratio for the poly glycol monomethyl ether described in lower aliphatic alcohols and step (2) stated is 1.5-4：1.
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